Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/91—Graft copolymers
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
  • C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
  • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/30—Materials not provided for elsewhere for aerosols
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q15/00—Anti-perspirants or body deodorants
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/005—Antimicrobial preparations
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S524/903—Aerosol compositions

Definitions

• This invention relates to aqueous aerosol film fozming compositions of matter and more particularly to nonfiammable aqueous aerosol compositions having improved storage stability, mechanical stability, corrosion inhibition and other properties.
• nonflamma-blle aqueous sprayable film forming compositions may be formulated by using a mixture of an aqueous emulsion of a graft copolymer of an N-vinyl lactam polymer having the formula ether, isobutyl vinyl ether, 2-oxyethyl vinyl ether, phenyl vinyl ether, methyl acrylate, ethyl acrylate, methyl methacryla te, Z-ethylhexyl acrylate, hexyl acrylate, styrene, methoxystyrene, ethylstyrene, chlorostyrene or the like with the polymer in the presence of a free radical supplying polymerization catalyst, and an aerosol propellent selected from the group consisting of a chlorofiuoroalkane hydrocarbon having from 1 to 2 carbon atoms and from 0 to 2 unreplaced
• N-vinyl lactam polymers characterized by Formula 1 are commercially available in a variety of forms, concentrations and molecular weights. ethods for the manufacture of these polymers are well known in the art.
• US. Patent 2,317,804 discloses a suitable method for preparing N-vinyl lactams.
• US. Patents 2,265,450 and 2,335,454 disclose methods for preparing N-vinyl lactam polymers and their aqueous solutions.
• N-vinyl lactams which may be employed to prcduce aqueous solution of N-vinyl lactam polymers for use in preparing graft copolymers for this invention include the N-vinyl derivatives of gamma, delta and epsilon lactams (N-vinyl derivatives of the cyclic amides of gamma, delta and epsilon amin-ocarboxylic acids of the aliphatic series) and the lower alkyl (methyl or ethyl) substituted derivatives of such lactams.
• N-vinyl-2- pyrrolidone (otherwise referred to as l-vinyl-2-pyrroldinone) is a preferred monomer.
• N-vinyl lactams operative herein, and which may be prepared in known manner by N-vinylation of the corresponding lactams at elevated temperatures in the manner di -closed in US. Patent 2,317,084, there may be mentioned the N-vinyl-substituted derivatives of the following lactams:
• Nonaqueous vinyl monomers which may be used in the preparation of N-vinyl lactam graft polymers include vinyl acetate, isopropenyl acetate, vinyl laurate, vinyl stearate, vinyl oleate, vinyl benzoate, vinyl chloride, 2- chloropropene, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether, 2-oxyethyl vinyl ether, methyl methacrylate, ethyl acrylate, 2- ethylhexyl acrylate, hexyl acrylate, doclecyl acrylate, octadecyl acrylate, styrene, 2-methoxystyrene, 2-methylstyrene, 2-chlorostyrene, 2-ethylstyrene
• a preferred group of vinyl monomers for use in preparing gnaft polymers of N-vinyl presence of a free radical supplying polymerization catalyst may range from about 400 to 2,000,000 or higher
• the molecular weight of the N-vinyl lactam polymer will depend on the degree of polymerization. Usually the degree of polymerization and the relative molecular weights of these polymers are expressed in terms of Fickentscher K values. The method of determining these values is given in Modern Plastics, 23, No. 3, 15761, 212, 214, 2l6, 2l8 (1945).
• N-vinyl lactam polymers having K vali'i'es of about 10 to 200 and preferably about to 60 or their mixtures are used in preparing graft copolymers for this invention.
• the graft copolymerization reaction is substantially quantitative in that emulsions are produced containing the N-vinyl lactam polymer-vinyl monomer copolymer in the dispersed nonaqueous phase with little or no polymeric products being dissolved in the continuous aqueous phase.
• the weight ratio of N- vinyl lactam polymer to vinyl monomer which is used in preparing these graft copolymers is optional depending on the desired properties, preferably ranging from about 5:95 to 60:40. Usually it is desirable to carry out the graft polymerization in such a manner that the finished aqueous emulsion contains from about 10 to 60% graft copolymer.
• N-vinyl lactam copolymers and other types of N-vinyl lactam polymers is illustrated schematically below in Formulas 2 to 6 inclusive wherein A represents a N-vinyl lactam monomer and B represents a dissimilar nonaqueous vinyl monomer.
• Aerosol formulations containing these emulsions form clear transparent films on glass plate. These films are essentially Water soluble and are also soluble to the extent of in benzene which indicates that the principal component in the emulsion is a graft copolymer and that little if any other polymeric products are dissolved in the aqueous phase. Aerosol formulations prepared with graft copolymers have excellent storage stabilities and long shelf lives. They also have improved mechanical stabilities.
• emulsions do not coagulate under stress and the spray nozzle does not clog even when the entire contents of the aerosol container are dispensed.
• These emulsions also have excellent emulsion stabilities in aerosol formulations. These aerosol emulsions can be easily reformed by mild agitation after they separate into two layers. The stability of these emulsion formulations may be further improved by incorporation of minor amounts of emulsifiers, stabilizers, viscosity modifiers or the like into the formulations.
• aerosolv formulations containing emulsions of random type copolymers obtained by polymerization of 1a N-vinyl lactam monomer and a dissimilar vinyl monomer in about the same proportions by the methods known in the prior art yield unstable aerosol emulsions when they are used under the same conditions in aerosol formulations. Since the emulsions of random type copolymers produced by the methods of the prior art may have viscosities as high as 75,000 cps. or more, they produce aerosol emulsion formulations which have viscosities that are too high to be satisfactory for :many purposes.
• aerosol formulations prepared with these copolymers produce opaque films on glass plate. Examination of these films indicates that the films are soluble only to the extent of 50% in benzene.
• the random type copolymers produced by the prior art are mixtures of water solube N-vinyl lactam polymers, benzene soluble vinyl polymers of the dissimilar vinyl monomer, water soluble random type copolymers and benzene soluble random type copolymers rather than a graft copolymer.
• the usual procedure employed in the formulation of aerosols with these random type copolymers is to evaporate water from the polymeric emulsion to obtain an anhydrous mixture of the copolymers.
• Emulsions of graft copolymers of N-vinyl lactam homopolymers may be formulated with aerosol propellents selected from the group consisting of a chlorofluoroalkane hydrocarbon from 1 to 2 carbon atoms and'from" to 2 unreplaced hydrogens, low boiling hydrocarbons having from 1 to 4 carbon atoms, nitrogen, nitrous ox'y- While any liquefiablefluoromethane, dichlorodifiuoromethane, monochlorotri-.
• aerosol propellents selected from the group consisting of a chlorofluoroalkane hydrocarbon from 1 to 2 carbon atoms and'from" to 2 unreplaced hydrogens, low boiling hydrocarbons having from 1 to 4 carbon atoms, nitrogen, nitrous ox'y- While any liquefiablefluoromethane, dichlorodifiuoromethane, monochlorotri-.
• fluoromethane monochlorodifluoromethane, trichlorodifluoroethane, trichloromonofluoroethane, dichlorodiflu-- oroethane, dichlorotetrafluoroethane, monochlorodifiu oroethane, trifluoroethyl chloride, their isomers or their mixtures.
• Low boiling hydrocarbons having from 1 to 4 carbon atoms may be used.
• Hydrocarbons such as methane, ethane, butane, their isomers and their mixtures may be employed. Normally these hydrocarbons are not used in aerosol formulations because they 'are flammable. However, in the present invention where aqueous emulsions of film forming materials are employed instead of solutions containing flammable solvents, these hydrocarbons may be used as propellents because the water present in the aqueous phase of the formulation suppresses flammability. Unsaturated hydrocarbons having from 1 to 4 carbons as well as their halogen derivatives may be used.
• Gases such as nitrogen, nitrous oxide and carbon dioxide may also be used. Although some of these gases require high pressures for compression, the pressure problem may be solved by the use of very strong containers or by storage at low temperatures. In certain applications, it may even be desirable to use mixtures of these gases with the halogenated or unsubstituted hydrocarbon described above.
• Example 1 An emulsion of the graft copolymer of N-vinyl-2-pyrrolidone polymer and styrene having a weight ratio of 50:50 and made as disclosed in Example 2 of Serial Number 69,571 filed November 16, 1960, using equal parts by weight of polyvinylpyrrolidone and styrene, is diluted with suflicient water to given an emulsion containing 2% of the graft copolymer solids. A 10 g. sample of the 2% graft copolymer is placed in a Fischer- Porter glass compatibility tube. The cold fill technique as described on pages 244 to 248 in Aerosol- Science and Technology, H. R.
• Example 2 A graft copolymer emulsion of N-vinyl-2-pyrrolidone polymer and styrene having a weight ratio of 30:70 and made as disclosed in Example 2 of Serial Number 69,571 filed November 16, 1960, using 3 parts of polyvinylpyrrolidone to 7 parts of styrene by weight, 23 parts are formulated with 0.5 part of a nonionic surfactant prepared by the reaction of 1.5 moles of ethylene oxide with 1 mole of nonylphenol and 0.5 part of polyethylene glycol fatty ester. This formulation produces a very stable emulsion.
• the emulsion is diluted with sufficient water to give an emulsion containing 5% of graft copolymer solids.
• a 60 g. sample of this 5% graft copolymer emulsion is placed in a Fischer-Porter glass compatibility tube.
• the cold fill technique described in Example 1 is used to add 30 g. of trichloromonofluoromethane and 2 0 g. of dichlorodifiuoromethane.
• the resulting aerosol mixture is a relatively stable homogeneous emulsion which slowly separates into two phases over 24 hours.
• the emulsion may be reformed readily by mild agitation after it separates into two layers.
• the spray qualities ofthe emulsion through a standard nozzle are excellent.
• a duplicate sample of the formulation is prepared and stored for six months. Examination of this sample after storage reveals that its spray qualities are comparable to those obtained with a freshly prepared sample.
• Example 3 An emulsion containing 40% of the graft copolymer of N-vinyl-2-pyrrolidone and ethyl acrylate having a weight ratio of :50 is used to prepare an aqueous nonflammable aerosol formulation following the procedure described in Example 1. Examination of the aerosol formulation reveals that it has excellent spray qualities, film forming properties and nonflammability properties. Laboratory evaluation shows that the formulation has excellent properties as a hair fixative. It produces films which have flexibility, rewettability and dispersability in excessive amounts of water as well as redrying properties.
• emulsions of graft copolymers of N-vinyl lactam homopolymers may be used in aqueous hair spray formulations.
• Other uses of these emulsions in aqueous aerosol formulations inelude fungicides, bactericides, antiseptics, sun tan sprays, anti-perspirants, deodorants, depilatories, hair tints, poi son ivy remedies, permanent hair waving solutions, skin freshener lotions, astringent lotions, insect bite lotions, insect repellents, metal cleaners, metal polishes, anti-foggants, glass cleaners, stain removers, starch glosses, mothproofers, shoe dressing preparations, leather cleaners, air deodorizers, antistatic agents, protective coatings, furniture polishes, shaving creams, floor waxes, sprayable bandages, or the like.
• the graft copolymer is used as a film forming agent to act as a matrix which holds the active ingredient in a fixed place so that the active ingredient will be more effective.
• One such application is where the graft copolymer is used in an insecticide formulation as an adhesive which holds particles of the insecticide on the treated surface to assure more effective use of the insecticide.
• a nonflammable aqueous sprayable film forming composition consisting essentially of (1) an aqueous emulsion of a graft copolymer of a N-vinyl lactam polymer of (Ill-CE;
• R is a member selected from the group consisting of hydrogen, methyl and ethyl
• R is a member selected from the group consisting of hydrogen, methyl and ethyl
• n is an integer of from 2 to 4
• m is an integer of from 4 to 20,000, prepared by reacting from 5 to 60 part by weight of the N-vinyl lactam polymer with from 95 to 40 parts by weight of a nonaqueous vinyl monomer selected from the group consisting of vinyl acetate, isopropenyl acetate, vinyl laurate, vinyl stearate, vinyl oleate, vinyl benzoate, vinyl chloride, 2-chloropropene, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, 2-oxyethyl vinyl ether,
• phenyl vinyl ether methyl acrylate, ethyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, hexyl acrylate, styrene, methoxystyrene, ethylstyrene and chlorostyrene, under polymerization conditions in the presence of a free radical supplying polymerization catalyst, and
• an aerosol propellent selected from the group consisting of a chlorofluoro alkane hydrocarbon having from 1 to 2 carbon atoms and from 0 to 2 unreplaced hydrogen atoms, a low boiling hydrocarbon having from 1 to 4 carbon atoms, nitrogen, nitrous oxide and carbon dioxide.
• composition as defined in claim 1 wherein the graft copolymer is a copolymer of N-vinyl-Z-pyrrolidone polymer and styrene having a weight ratio of 50:50.
• composition as defined in claim 1 wherein the graft copolymer is a copolymer of N-vinyl-Z-pyrrolidone polymer and styrene having a weight ratio of :70.
• composition as defined in claim 1 wherein the graft copolymer is a copolymer of N-vinyl-Z-pyrrolidone and ethyl acrylate having a weight ratio of :50.

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Citations (3)

• 1964
  • 1964-05-12 US US366900A patent/US3301808A/en not_active Expired - Lifetime
• 1965
  • 1965-05-12 CH CH657365A patent/CH469752A/de unknown
  • 1965-05-12 BE BE663786D patent/BE663786A/xx unknown

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